Elucidation of the electronic structure of molecules with the help of NMR spin-spin coupling constants: the FH molecule

Jürgen Gräfenstein, Tell Tuttle, Dieter Cremer

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

It is demonstrated how the one-bond NMR spin-spin coupling constant (SSCC) 1J(FH) can be used as a source of information on the electronic structure of the FH molecule. For this purpose, the best possible agreement between measured and calculated SSCC is achieved by large basis set coupled perturbed density functional theory calculations. Then, the calculated value is dissected into its four Ramsey terms: Fermi contact, the paramagnetic spin-orbit term, the diamagnetic spin-orbit term, and the spin dipole term, which in turn are decomposed into orbital contributions and then described by their spin densities and orbital current densities. In this way, the SSCC gives detailed information about the electronegativity of F, the bond polarity, the bond polarizability, the volume and the polarizability of σ and π lone pair orbitals, the s- or p-character of the bond orbital, the nature of the LUMO, and the density distribution around F.

Original languageEnglish
Pages (from-to)2325-2339
Number of pages15
JournalJournal of Physical Chemistry A
Volume109
Issue number10
Early online date22 Feb 2005
DOIs
Publication statusPublished - 17 Mar 2005

Keywords

  • spin-spin coupling constants
  • SSCCs
  • FH molecule
  • Fermi contact spin coupling

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